Golf ball with very thick cover

ABSTRACT

Disclosed herein is a golf ball having a solid core with a coefficient of restitution of at least 0.650 and a cover with a thickness of at least 3.6 mm (0.142 inches) and a Shore D hardness of at least 60. The combination of a soft core with a thick, hard cover results in a ball having better distance than conventional golf balls having a comparable coefficient of restitution.

This Application is a continuation of U.S. application Ser. No.08/743,579 filed Nov. 4, 1996, U.S. Pat. No. 5,833,553 now allowed,which is a continuation-in-part of U.S. application Ser. No. 08/240,259filed May 10, 1994, now abandoned, which is a continuation-in-part ofU.S. application Ser. No. 08/054,406, filed Apr. 28, 1993 (U.S. Pat. No.5,368,304).

BACKGROUND OF THE INVENTION

The present invention relates to golf balls, and more particularly togolf balls having thick covers.

Spin rate is an important golf ball characteristic for both the skilledand unskilled golfer. High spin rates allow for the more skilled golfer,such as PGA professionals and low handicap players, to maximize controlof the golf ball. This is particularly beneficial to the more skilledgolfer when hitting an approach shot to a green. The ability tointentionally produce "back spin", thereby stopping the ball quickly onthe green, and/or "side spin" to draw or fade the ball, substantiallyimproves the golfer's control over the ball. Thus, the more skilledgolfer generally prefers a golf ball exhibiting high spin rateproperties.

However, a high spin golf ball is not desired by all golfers,particularly high handicap players who cannot intentionally control thespin of the ball. In this regard, less skilled golfers, have, amongothers, two substantial obstacles to improving their game: slicing andhooking. When a club head meets a ball, an unintentional side spin isoften imparted which sends the ball off its intended course. The sidespin reduces one's control over the ball as well as the distance theball will travel. As a result, unwanted strokes are added to the game.

Consequently, while the more skilled golfer desires a high spin golfball, a more efficient ball for the less skilled player is a golf ballthat exhibits low spin properties. The low spin ball reduces slicing andhooking and enhances roll distance for the amateur golfer. It would beuseful to develop a low spin golf ball with excellent distance for useby high handicap players.

SUMMARY OF THE INVENTION

An object of the invention is to provide a golf ball with a low spinrate.

Another object of the invention is to provide a golf ball having betterdistance than conventional golf balls having a comparable coefficient ofrestitution.

Another object of the invention is to provide a golf ball having a lowspin rate and excellent distance on full shots, combined with a softfeel when the ball is used for chipping and putting.

Yet another object of the invention is to provide a method of making agolf ball of the type described above.

The invention in a preferred form is a golf ball comprising a solid corehaving a coefficient of restitution (COR) of at least 0.650, and a coverhaving a thickness of at least 3.6 mm (when measured at a land area ofthe cover) and a Shore D hardness (measured generally in accordance withA.S.T.M. D-2240, but measured on the land area of a curved surface of amolded ball) of at least 60, preferably at least 64.

In one embodiment of the invention, the cover includes an inner coverlayer and an outer cover layer. The inner and outer cover layerspreferably have substantially the same Shore D hardness.

The golf ball preferably has a cover thickness of at least 3.8 mm, evenmore preferably at least 4.0 mm, and most preferably at least 4.5 mmwhen measured at a land area of the cover. The core preferably has a CORof at least 0.700 and more preferably at least 0.750. The differencebetween the coefficient of restitution of the ball and the coefficientof restitution of the core is at least 0.025. The core preferably has aPGA compression of about 85 or less.

Another preferred form of the invention is a method of making a golfball comprising forming a core having a COR of at least 0.650 andforming a cover over the core, the cover having a thickness of at least3.6 mm (when measured at a land area of the cover) and a Shore Dhardness (measured generally in accordance with A.S.T.M. D-2240, butmeasured on a land area of a curved surface of a molded ball) of atleast 60, and preferably at least 64. The core preferably has a PGAcompression of 85 or less.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross section of a two-piece solid golf ball according tothe invention.

FIG. 2 shows a cross section of a three-piece solid golf ball accordingto the invention.

DETAILED DESCRIPTION OF THE INVENTION

The golf ball of the invention has a solid core having a COR of at least0.650 in combination with a thick, relatively hard cover.

Referring to the drawings and particularly to FIG. 1, a first preferredembodiment of a golf ball according to the invention is shown and isdesignated as 10. The golf ball has a solid or foam core 12. A cover 14surrounds the core.

In a preferred embodiment, the core 12 is relatively soft, with a PGAcompression of about 85 or less, preferably about 20 to 85, and morepreferably about 40-60. The cover 14 has a thickness of at least 3.6 mm(0.142 inches). It is particularly preferred that the cover thickness beat least 3.8 mm (0.150 inches). Particularly good results are obtainedwhen the cover has a thickness of at least 4.0 mm (0.157 inches). Incertain circumstances, such as when a harder compression and harder feelmay be desired, it is optimum to employ a cover having a thickness of atleast 4.5 mm (0.177 inches). As used herein, "cover thickness" is thethickness of the cover from the inner diameter of the cover to the outersurface of the cover at a land area.

The golf ball of the invention has a difference between the coefficientof restitution of the ball and the coefficient of restitution of thecore of at least 0.025, preferably at least 0.035, and more preferablyat least 0.045. The golf balls have an unexpectedly long distance giventheir coefficient of restitution.

As used herein, "Shore D hardness" of a cover is measured generally inaccordance with ASTM D-2240, except the measurements are made on thecurved surface of a molded cover, rather than on a plaque. Furthermore,the Shore D hardness of the cover is measured while the cover remainsover the core. When a hardness measurement is made on a dimpled cover,Shore D hardness is measured at a land area of the dimpled cover.

The cover 14 has a Shore D hardness of 60 or more, and preferably atleast 64. The composition of cover 14 preferably but not necessarilyincludes a hard, high stiffness, preferably but not necessarily highacid ionomer such as that sold by E.I. DuPont de Nemours & Company underthe trademark "Surlyn®" and by Exxon Corporation under the tradename"lotek", or blends thereof. In addition to the Surlyn® and lotekionomers, the cover may comprise any ionomer or other impact resistantmaterial which either alone or in combination with ionomers, such as inhard/soft blends, produces a molded cover having a Shore D hardness ofat least 60, and preferably at least 64. Preferable cover materialsinclude, for example, zinc, sodium and lithium ionomers, and blends ofionomers with harder non-ionic polymers such as nylon, polyphenyleneoxide, metallocene catalyzed polyolefins, and other compatiblethermoplastics. Examples of cover compositions which may be used are setforth in detail in copending U.S. Ser. No. 08/596,690, which is acontinuation of U.S. Ser. No. 08/174,765, which in turn is acontinuation of U.S. Ser. No. 07/776,803 filed Oct. 15, 1991, and U.S.Ser. No. 08/493,089, which is a continuation of 07/981,751, which inturn is a continuation of U.S. Ser. No. 07/901,660 filed Jun. 19, 1992,both incorporated herein by reference. Of course, the cover compositionsare not limited in any way to the compositions set forth in saidcopending applications.

The cover and/or core may include fillers which include, but are notlimited to, clay, talc, asbestos, graphite, glass, mica, calciummetasilicate, barium sulfate, zinc sulfide, aluminum hydroxide,silicates, diatomaceous earth, carbonates such as calcium carbonate,magnesium carbonate and the like, metals such as titanium, tungsten,aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron,bronze, cobalt and beryllium, and alloys of the above metals, metaloxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide,magnesium oxide, zirconium oxide and the like, particulate syntheticplastic such as high molecular weight polyethylene, polystyrene,polyethylene ionomer resins and the like, particulate carbonaceousmaterials such as carbon black, natural bitumen and the like, as well ascotton flock, cellulose flock, and leather fiber. Dark colored fillersgenerally are not preferred for use at the outer surface of the ball ifa white ball is desired. Thus, a two-layer cover in which a non-whitefiller is only present in the inner cover layer can be employed. Theamount of filler employed is primarily a function of weightrestrictions. For example, weight may be removed from the core andplaced in the inner and/or outer cover. This added weight will changethe moment of inertia of the ball thereby potentially alteringperformance. Whereas typically the specific gravity of the cover layeror layers is about 0.95-1.00, it may be desirable to increase thespecific gravity of one or more of the cover layers to greater than 1.0,preferably 1.1-2.0.

A second embodiment of a golf ball according to the invention is shownin FIG. 2, and is designated as 10'. The ball 10' has a core 12' whichis a substantially solid material, as is illustrated in FIG. 2. The core12' preferably has a PGA compression of about 85 or less, preferably 20to 85, and more preferably 40-60. A multi-layer cover 14' having two ormore layers is formed over the core 12'. In the embodiment shown, thecover 14' includes two layers, namely an inner cover layer 16' and anouter cover layer 18'. The inner and outer cover layers havesubstantially the same Shore D hardness. In other words, the differencebetween the Shore D hardness of the inner cover layer 16' and outercover layer 18' is 5 or less, and preferably is 2 or less. Each of theinner and outer layers 16' and 18' has a Shore D hardness of at least64. The overall thickness of the inner and outer cover layers is thesame as the thickness of the cover 14 of the embodiment of FIG. 1. Eachof the 2 or more cover layers is at least 0.25 mm thick (0.010 inches)and typically is 0.64 to 6.4 mm (0.025 to 0.250 inches) thick, morepreferably 1.3 to 5.1 mm (0.051-0.020 inches) thick. The inner and outercover layers 16' and 18' preferably are formed from the samecomposition, and preferably comprise ionomer, ionomer blends, or filledor reinforced ionomers.

As suggested above, two principal properties involved in golf ballperformance are resilience and PGA compression. Resilience is determinedby the coefficient of restitution (C.O.R.), the constant "e" which isthe ratio of the relative velocity of an elastic sphere after directimpact to that before impact. As a result, the coefficient ofrestitution ("e") can vary from 0 to 1, with 1 being equivalent to aperfectly or completely elastic collision and 0 being equivalent to aperfectly or completely inelastic collision.

Resilience (C.O.R.), along with additional factors such as club headspeed, angle of trajectory and ball configuration (i.e., dimple pattern)generally determine the distance a ball will travel when hit. Since clubhead speed and the angle of trajectory are factors not easilycontrollable by a manufacturer, factors of concern among manufacturersare the coefficient of restitution (C.O.R.) and the surfaceconfiguration of the ball.

The coefficient of restitution (C.O.R.) in solid core balls is afunction of the composition of the molded core and of the cover. Inballs containing a wound core (i.e., balls comprising a liquid or solidcenter, elastic windings, and a cover), the coefficient of restitutionis a function of not only the composition of the center and cover, butalso the composition and tension of the elastomeric windings. Althoughboth the core and the cover contribute to the coefficient ofrestitution, the present invention is directed to the enhancedcoefficient of restitution (and thus travel distance) which is affectedby the cover composition.

The coefficient of restitution is the ratio of the outgoing velocity tothe incoming velocity. In the examples of this application, thecoefficient of restitution of a golf ball was measured by propelling aball horizontally at a speed of 125±1 feet per second (fps) against agenerally vertical, hard, flat steel plate and measuring the ball'sincoming and outgoing velocity electronically. Speeds were measured witha pair of Ohler Mark 55 ballistic screens, which provide a timing pulsewhen an object passes through them. The screens are separated by 36" andare located 25.25" and 61.25" from the rebound wall. The ball speed wasmeasured by timing the pulses from screen 1 to screen 2 on the way intothe rebound wall (as the average speed of the ball over 36"), and thenthe exit speed was timed from screen 2 to screen 1 over the samedistance. The rebound wall was tilted 2 degrees from a vertical plane toallow the ball to rebound slightly downward in order to miss the edge ofthe cannon that fired it.

As indicated above, the incoming speed should be 125+/-1 fps.Furthermore, the correlation between COR and forward or incoming speedhas been studied and a correction has been made over the +/-1 fps rangeso that the COR is reported as if the ball had an incoming speed ofexactly 125.0 fps.

The coefficient of restitution must be carefully controlled in allcommercial golf balls if the ball is to be within the specificationsregulated by the United States Golf Association (U.S.G.A.). Along thisline, the U.S.G.A. standards indicate that a "regulation" ball cannothave an initial velocity (i.e., the speed off the club) exceeding 255feet per second. Since the coefficient of restitution of a ball isrelated to the ball's initial velocity, it is highly desirable toproduce a ball having sufficiently high coefficient of restitution toclosely approach the U.S.G.A. limit on initial velocity, while having anample degree of softness (i.e., hardness) to produce enhancedplayability (i.e., spin, etc.).

As indicated above, PGA compression is another important propertyinvolved in the performance of a golf ball. The compression of the ballcan affect the playability of the ball on striking and the sound or"click" produced. PGA compression is generally equal to 160 minus Riehlecompression.

The specially produced core compositions and resulting molded cores ofthe preferred embodiment of the present invention are preferablymanufactured using relatively conventional techniques. In this regard,the core compositions of the invention may be based on polybutadiene,natural rubber, metallocene catalyzed polyolefins such as EXACT (ExxonChem. Co.) and ENGAGE (Dow Chem. Co.), polyurethanes, otherthermoplastic or thermoset elastomers, and mixtures of one or more ofthe above materials with each other and/or with other elastomers. Thecore may be formed from a uniform composition or may be a dual ormulti-layer core. The core may be foamed or unfoamed. It is preferredthat the base elastomer have a relatively high molecular weight.Polybutadiene has been found to be particularly useful because itimparts to the golf balls a relatively high coefficient of restitution.Polybutadiene can be cured using a free radical initiator such as aperoxide, or can be sulfur cured. A broad range for the molecular weightof preferred base elastomers is from about 50,000 to about 500,000. Amore preferred range for the molecular weight of the base elastomer isfrom about 100,000 to about 500,000. As a base elastomer for the corecomposition, cis-1-4-polybutadiene is preferably employed, or a blend ofcis-1-4-polybutadiene with other elastomers may also be utilized. Mostpreferably, cis-1-4-polybutadiene having a weight-average molecularweight of from about 100,000 to about 500,000 is employed. Along thisline, it has been found that the high cis-1-4-polybutadienesmanufactured and sold by Bayer Corp., Germany, under the trade nameTaktene 220 or 1220 are particularly preferred. Furthermore, the coremay be comprised of a crosslinked natural rubber, EPDM, metallocenecatalyzed polyolefin, or another crosslinkable elastomer.

When polybutadiene is used for golf ball cores, it commonly iscrosslinked with an unsaturated carboxylic acid co-crosslinking agent.The unsaturated carboxylic acid component of the core compositiontypically is the reaction product of the selected carboxylic acid oracids and an oxide or carbonate of a metal such as zinc, magnesium,barium, calcium, lithium, sodium, potassium, cadmium, lead, tin, and thelike. Preferably, the oxides of polyvalent metals such as zinc,magnesium and cadmium are used, and most preferably, the oxide is zincoxide.

Exemplary of the unsaturated carboxylic acids which find utility in thecore compositions are acrylic acid, methacrylic acid, itaconic acid,crotonic acid, sorbic acid, and the like, and mixtures thereof.Preferably, the acid component is either acrylic or methacrylic acid.Usually, from about 5 to about 40, and preferably from about 15 to about30 parts by weight of the carboxylic acid salt, such as zinc diacrylate,is included in the core composition. The unsaturated carboxylic acidsand metal salts thereof are generally soluble in the elastomeric base,or are readily dispersible.

The free radical initiator included in the core composition is any knownpolymerization initiator (a co-crosslinking agent) which decomposesduring the cure cycle. The term "free radical initiator" as used hereinrefers to a chemical which, when added to a mixture of the elastomericblend and a metal salt of an unsaturated, carboxylic acid, promotescrosslinking of the elastomers by the metal salt of the unsaturatedcarboxylic acid. The amount of the selected initiator present isdictated only by the requirements of catalytic activity as apolymerization initiator. Suitable initiators include peroxides,persulfates, azo compounds and hydrazides. Peroxides which are readilycommercially available are conveniently used in the present invention,generally in amounts of from about 0.1 to about 10.0 and preferably inamounts of from about 0.3 to about 3.0 parts by weight per each 100parts of elastomer.

Exemplary of suitable peroxides for the purposes of the presentinvention are dicumyl peroxide, n-butyl 4,4'-bis (butylperoxy) valerate,1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, di-t-butyl peroxideand 2,5-di-(t-butylperoxy)-2,5 dimethyl hexane and the like, as well asmixtures thereof. It will be understood that the total amount ofinitiators used will vary depending on the specific end product desiredand the particular initiators employed.

Examples of such commercially available peroxides are Luperco 230 or 231XL sold by Atochem, Lucidol Division, Buffalo, N.Y., and Trigonox 17/40or 29/40 sold by Akzo Chemicals, America, Chicago, Ill. In this regardLuperco 230 XL and Trigonox 29/40 are comprised of1,1-bis(t-butylperoxy-3,3,5-trimethyl cyclohexane. The one hour halflife of Luperco 231 XL is about 112° C., and the one hour half life ofTrigonox 29/40 is about 129° C.

The core compositions of the present invention may additionally containany other suitable and compatible modifying ingredients including, butnot limited to, metal oxides, fatty acids, and diisocyanates andpolypropylene powder resin. For example, Papi 94, a polymericdiisocyanate, commonly available from Dow Chemical Co., Midland, Mich.,is an optional component in the rubber compositions. It can range fromabout 0 to 5 parts by weight per 100 parts by weight rubber (phr)component, and acts as a moisture scavenger. In addition, it has beenfound that the addition of a polypropylene powder resin results in acore which is hard (i.e. exhibits high PGA compression) and thus allowsfor a reduction in the amount of crosslinking co-agent utilized tosoften the core to a normal or below normal compression.

Furthermore, because polypropylene powder resin can be added to a corecomposition without an increase in weight of the molded core uponcuring, the addition of the polypropylene powder allows for the additionof higher specific gravity fillers, such as mineral fillers. Since thecrosslinking agents utilized in the polybutadiene core compositions areexpensive and/or the higher specific gravity fillers are relativelyinexpensive, the addition of the polypropylene powder resinsubstantially lowers the cost of the golf ball cores while maintaining,or lowering, weight and compression.

The polypropylene (C₃ H₅) powder suitable for use in the presentinvention has a specific gravity of about 0.90 g/cm³, a melt flow rateof about 4 to about 1 2 and a particle size distribution of greater than99% through a 20 mesh screen. Examples of such polypropylene powderresins include those sold by the Amoco Chemical Co., Chicago, Ill.,under the designations "6400 P", "7000 P" and "7200 P". Generally, from0 to about 25 parts by weight polypropylene powder per each 100 parts ofelastomer are included in the present invention.

Various activators may also be included in the compositions of thepresent invention. For example, zinc oxide and/or magnesium oxide areactivators for the polybutadiene. The activator can range from about 2to about 30 parts by weight per 100 parts by weight of the rubbers (phr)component.

Moreover, reinforcement agents may be added to the core compositions ofthe present invention. Since the specific gravity of polypropylenepowder is very low, and when compounded, the polypropylene powderproduces a lighter molded core, when polypropylene is incorporated inthe core compositions, relatively large amounts of higher specificgravity fillers may be added so long as the specific core weightlimitations are met. As indicated above, additional benefits may beobtained by the incorporation of relatively large amounts of higherspecific gravity, inexpensive mineral fillers such as calcium carbonate.Such fillers as are incorporated into the core compositions should be infinely divided form, as for example, in a size generally less than about30 mesh and preferably less than about 100 mesh U.S. standard size. Theamount of additional filler included in the core composition isprimarily dictated by weight restrictions and preferably is included inamounts of from about 10 to about 100 parts by weight per 100 partsrubber.

The preferred fillers are relatively inexpensive and heavy and serve tolower the cost of the ball and to increase the weight of the ball toclosely approach the U.S.G.A. weight limit of 1.620 ounces. However, ifthicker cover compositions are to be applied to the core to producelarger than normal (i.e. greater than 1.680 inches in diameter) balls,use of such fillers and modifying agents will be limited in order tomeet the U.S.G.A. maximum weight limitations of 1.620 ounces. Limestoneis ground calcium/magnesium carbonate and is used because it is aninexpensive, heavy filler. Ground flash filler may be incorporated andis preferably 20 mesh ground up center stock from the excess flash fromcompression molding. It lowers the cost and may increase the hardness ofthe ball.

Fatty acids or metallic salts of fatty acids may also be included in thecompositions, functioning to improve moldability and processing.Generally, free fatty acids having from abut 10 to about 40 carbonatoms, and preferably having from about 15 to about 10 carbon atoms, areused. Exemplary of suitable fatty acids are stearic acid and linoleicacids, as well as mixtures thereof. Exemplary of suitable metallic saltsof fatty acids include zinc stearate. When included in the corecompositions, the metallic salts of fatty acids are present in amountsof from about 1 to about 25, preferably in amounts from about 2 to about15 parts by weight based on 100 parts rubber (elastomer). It ispreferred that the core compositions include stearic acid as the fattyacid adjunct in an amount of from about 2 to about 5 parts by weight per100 parts of rubber.

Diisocyanates may also be optionally included in the core compositionswhen utilized, the diisocyanates are included in amounts of from about0.2 to about 5.0 parts by weight based on 100 parts rubber. Exemplary ofsuitable diisocyanates is 4,4'-diphenylmethane diisocyanate and otherpolyfunctional isocyanates known to the art.

Furthermore, the dialkyl tin difatty acids set forth in U.S. Pat. No.4,844,471, the dispensing agents disclosed in U.S. Pat. No. 4,838,556,and the dithiocarbamates set forth in U.S. Pat. No. 4,852,884 may alsobe incorporated into the polybutadiene compositions of the presentinvention. The specific types and amounts of such additives are setforth in the above identified patents, which are incorporated herein byreference.

The core compositions of the invention which contain polybutadiene aregenerally comprised of 100 parts by weight of a base elastomer (orrubber) selected from polybutadiene and mixtures of polybutadiene withother elastomers, 15 to 25 parts by weight of at least one metallic saltof an unsaturated carboxylic acid, and 0.5 to 10 parts by weight of afree radical initiator.

As indicated above, additional suitable and compatible modifying agentssuch as particulate polypropylene resin, fatty acids, and secondaryadditives such as pecan shell flour, ground flash (i.e. grindings frompreviously manufactured cores of substantially identical construction),barium sulfate, zinc oxide, etc. may be added to the core compositionsto adjust the weight of the ball as necessary in order to have thefinished molded ball (core, cover and coatings) to closely approach theU.S.G.A. weight limit of 1.620 ounces.

In producing solid golf ball cores utilizing the present compositions,the ingredients may be intimately mixed using, for example, two rollmills or an internal mixer until the composition is uniform, usuallyover a period of from about 5 to about 20 minutes. The sequence ofaddition of components is not critical. A preferred blending sequence isas follows.

The elastomer, polypropylene powder resin (if desired), fillers, zincsalt, metal oxide, fatty acid, and the metallic dithiocarbamate (ifdesired), surfactant (if desired), and tin difatty acid (if desired),are blended for about 7 minutes in an internal mixer such as a Banbury®(Farrel Corp.) mixer. As a result of shear during mixing, thetemperature rises to about 200° F. The initiator and diisocyanate arethen added and the mixing continued until the temperature reaches about220° F. whereupon the batch is discharged onto a two roll mill, mixedfor about one minute and sheeted out.

The sheet is rolled into a "pig" and then placed in a Barwell preformerand slugs are produced. The slugs are then subjected to compressionmolding at about 320° F. for about 14 minutes. After molding, the moldedcores are cooled, the cooling effected at room temperature for about 4hours or in cold water for about one hour. The molded cores can besubjected to a centerless grinding operation whereby a thin layer of themolded core is removed to produce a round core having a diameter of 1.2to 1.5 inches. Alternatively, the cores are used in the as-molded statewith no grinding needed to achieve roundness.

The mixing is desirably conducted in such a manner that the compositiondoes not reach incipient polymerization temperatures during the blendingof the various components.

Usually the curable component of the composition will be cured byheating the composition at elevated temperatures on the order of fromabout 275° F. to about 350° F., preferably and usually from about 290°F. to about 325° F., with molding of the composition effectedsimultaneously with the curing thereof. The composition can be formedinto a core structure by any one of a variety of molding techniques,e.g. injection, compression, or transfer molding. When the compositionis cured by heating, the time required for heating will normally beshort, generally from about 10 to about 20 minutes, depending upon theparticular curing agent used. Those of ordinary skill in the artrelating to free radical curing agents for polymers are conversant withadjustments of cure times and temperatures required to effect optimumresults with any specific free radical agent.

After molding, the core is removed from the mold and the surface thereofoptionally is treated to facilitate adhesion thereof to the coveringmaterials. Surface treatment can be effected by any of the severaltechniques known in the art, such as corona discharge, ozone treatment,sand blasting, and the like. Preferably, surface treatment is effectedby grinding with an abrasive wheel. As indicated above, the cover of thegolf ball preferably but not necessarily comprises an ionomer. High orlow acid ionomers, or ionomer blends can be used. The high acid ionomerswhich may be suitable for use in formulating the cover compositions areionic copolymers which are the metal, i.e., sodium, zinc, magnesium,lithium, etc., salts of the reaction product of an olefin having fromabout 2 to 8 carbon atoms and an unsaturated monocarboxylic acid havingfrom about 3 to 8 carbon atoms. Preferably, the ionomeric resins arecopolymers of ethylene and either acrylic or methacrylic acid. In somecircumstances, an additional comonomer such as an acrylate ester (i.e.,iso- or n-butylacrylate, etc.) can also be included to produce a softerterpolymer. The carboxylic acid groups of the copolymer are at leastpartially neutralized (i.e., approximately 10-100%, preferably 30-70%)by the metal ions. Each of the high acid ionomer resins contains greaterthan about 16% by weight of a carboxylic acid, preferably from about 17%to about 25% by weight of a carboxylic acid, more preferably from about18.5% to about 21.5% by weight of a carboxylic acid.

The high acid ionomeric resins available from Exxon under thedesignation "lotek", are somewhat similar to the high acid ionomericresins available under the "Surlyn®" trademark. However, since the lotekionomeric resins are sodium, lithium or zinc salts ofpoly(ethylene-acrylic acid) and the "Surlyn®" resins are zinc, sodium,lithium, etc. salts of poly(ethylene-methacrylic acid), distinctdifferences in properties exist.

Non-limiting examples of the high acid methacrylic acid based ionomerssuitable for use in accordance with this invention include Surlyn® 8140(Na), 8220 (Na), 8240 (Na), 9120 (Zn), 9220 (Zn), AD8181 (Li), AD8530(Zn), AD8531 (Na) and SEP 671 (Li).

    ______________________________________                                                       SURLYN ®                                                                            SURLYN ®                                                        8140      9120                                                                (19 wt % acid)                                                                          (19 wt % acid)                                       ______________________________________                                        IONOMER                                                                       Cation           Na          Zn                                               Melt Flow index, g/10 min.                                                                     2.6         1.3                                              Specific gravity 0.96        0.97                                             MP, ° C.  88          85                                               FP, ° C.  49          50                                               MECHANICAL PROPERTIES                                                         Tensile Strength, kpsi (MPa)                                                                   5.0 (34.5)  3.8 (26.2)                                       Yield Strength, kpsi (MPa)                                                                     2.8 (19.3)  2.4 (16.6)                                       Elongation, %    340         280                                              Flex Mod, kpsi (MPa)                                                                           71 (490)    84 (440)                                         Shore D Hardness 70          69                                               ______________________________________                                    

Examples of the high acid acrylic acid based ionomers suitable for usein the present invention also include lotek high acid ethylene acrylicacid ionomers produced by Exxon such as 1001, 1002, 959, 960, 989, 990,1003, 1004, 993, and 994. In this regard, lotek 959 is a sodium ionneutralized ethylene-acrylic acid copolymer. According to Exxon, loteks959 and 960 contain from about 19.0 to about 21.0% by weight acrylicacid with approximately 30 to about 70 percent of the acid groupsneutralized with sodium and zinc ions, respectively. The physicalproperties of these and other high acid acrylic acid based ionomers areas follows:

                  TABLE 2                                                         ______________________________________                                        lotek Resins                                                                  ______________________________________                                        PROPERTY    1001   1002   959   1003 1004 960                                 ______________________________________                                        Melt index, 1.0    1.6    2.0   1.1  2.0  1.8                                 g/10 min.                                                                     Cation      Na     Na     Na    Zn   Zn   Zn                                  Melting point,                                                                            183    183    172   180  180.5                                                                              174                                 ° F.                                                                   Crystallization                                                                           107    110    106   125  126.5                                                                              120                                 point, ° F.                                                            Vicat       125    125    130   133  131  131                                 Softening                                                                     Point, ° F.                                                            Tensile @   34.4   31.7   4600  24.8 20.6 3500                                Break       MPa    MPa    psi   MPa  MPa  psi                                 Tensile @   21.8   22.5   --    14.9 14.0 --                                  Yield       MPa    MPa          MPa  MPa                                      1% Secant   356    418    350   145  128  140                                 Modulus     MPa    MPa    MPa   MPa  MPa  MPa                                 Elongation  341    348    325   387  437  430                                 @ Break, %                                                                    Hardness,   63     62     66    54   53   57                                  Shore D                                                                       Flexural    365    380    66,000                                                                              147  130  27,000                              Modulus     MPa    MPa    psi   MPa  MPa  psi                                 Density     .9558  .9557  .968  .9715                                                                              .9691                                                                              .980                                            g/cm.sup.3                                                                           g/cm.sup.3                                                                           g/cm.sup.3                                                                          g/cm.sup.3                                                                         g/cm.sup.3                                                                         g/cm.sup.3                          ______________________________________                                                              EX      EX   EX    EX                                                         989     993  994   990                                  ______________________________________                                        Melt index   g/10 min 1.30    1.25 1.32  1.24                                 Moisture     ppm      482     214  997   654                                  Cation Type  --       Na      Li   K     Zn                                   M + content by AAS                                                                         wt %     2.74    0.87 4.54  0                                    Zn content by AAS                                                                          wt %     0       0    0     3.16                                 Density      kg/m.sup.3                                                                             959     945  976   977                                  Vicat softening point                                                                      ° C.                                                                            52.5    51   50    55.0                                 Crystallization point                                                                      ° C.                                                                            40.1    39.8 44.9  54.4                                 Melting point                                                                              ° C.                                                                            82.6    81.0 80.4  81.0                                 Tensile at yield                                                                           MPa      23.8    24.6 22    16.5                                 Tensil at break                                                                            MPa      32.3    31.1 29.7  23.8                                 Elongation at break                                                                        %        330     260  340   357                                  1% secant modulus                                                                          MPa      389     379  312   205                                  Flexural modulus                                                                           MPa      340     368  303   183                                  Abrasion resistance                                                                        mg       20.0    9.2  15.2  20.5                                 Hardness Shore D                                                                           --       62      62.5 61    56                                   Zwick rebound                                                                              %        61      63   59    48                                   ______________________________________                                    

Furthermore, as a result of the development by the assignee of thisapplication of a number of new ionomers neutralized to various extentsby several different types of metal cations, such as by manganese,lithium, potassium, calcium and nickel cations, several new ionomersand/or ionomer blends besides sodium, zinc and magnesium high acidionomers or ionomer blends are now available for golf ball coverproduction. In particular it has been found that new cation neutralizedhigh acid ionomer blends produce inner cover layer compositionsexhibiting enhanced hardness and resilience due to synergies which occurduring processing. Consequently, the metal cation neutralized high acidionomer resins recently produced can be blended to produce substantiallyhigher C.O.R.'s than those produced by the low acid ionomer inner covercompositions presently commercially available.

More particularly, several new metal cation neutralized high acidionomer resins have been produced by the inventor by neutralizing, tovarious extents, high acid copolymers of an alpha-olefin and an alpha,beta-unsaturated carboxylic acid with a wide variety of different metalcation salts. It has been found that numerous new metal cationneutralized high acid ionomer resins can be obtained by reacting a highacid copolymer (i.e. a copolymer containing greater than 16% by weightacid, preferably from about 17 to about 25 weight percent acid, and morepreferably about 20 weight percent acid), with a metal cation saltcapable of ionizing or neutralizing the copolymer to the extent desired(i.e. from about 10% to 90%).

The base copolymer is made up of greater than 16% by weight of an alpha,beta-unsaturated carboxylic acid and an alpha-olefin. As indicatedabove, a softening comonomer can be included in the copolymer.Generally, the alpha-olefin has from 2 to 10 carbon atoms and ispreferably ethylene, and the unsaturated carboxylic acid is a carboxylicacid having from about 3 to 8 carbons. Examples of such acids includeacrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid,crotonic acid, maleic acid, fumaric acid, and itaconic acid, withacrylic acid being preferred.

The softening comonomer that can be optionally included in the innercover layer for the golf ball of the invention may be selected from thegroup consisting of vinyl esters of aliphatic carboxylic acids whereinthe acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkylgroups contains 1 to 10 carbon atoms, and alkyl acrylates ormethacrylates wherein the alkyl group contains 1 to 10 carbon atoms.Suitable softening comonomers include vinyl acetate, methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,butyl methacrylate, or the like.

Consequently, examples of a number of copolymers suitable for use toproduce the high acid ionomers included in the present inventioninclude, but are not limited to, high acid embodiments of anethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer,an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer,an ethylene/methacrylic acid/vinyl acetate copolymer, anethylene/acrylic acid/vinyl alcohol copolymer, etc. The base copolymerbroadly contains greater than 16% by weight unsaturated carboxylic acid,from about 39 to about 83% by weight ethylene and from 0 to about 40% byweight of a softening comonomer. Preferably, the copolymer containsabout 20% by weight unsaturated carboxylic acid and about 80% by weightethylene. Most preferably, the copolymer contains about 20% acrylic acidwith the remainder being ethylene.

Along these lines, examples of the preferred high acid base copolymerswhich fulfill the criteria set forth above, are a series ofethylene-acrylic copolymers which are commercially available from TheDow Chemical Company, Midland, Mich., under the "Primacor" designation.These high acid base copolymers exhibit the typical properties set forthbelow in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Typical Properties of Primacor                                                Ethylene-Acrylic Acid Copolymers                                                               MELT TENSILE                                                                            FLEXURAL                                                                            VICAT                                             PERCENT                                                                             DENSITY,                                                                            INDEX                                                                              YD. ST                                                                             MODULUS                                                                             SOFT PT                                                                            SHORE D                                 GRADE                                                                              ACID  g/cc  g/10 min                                                                           (psi)                                                                              (psi) (° C.)                                                                      HARDNESS                                __________________________________________________________________________    ASTM       D-792 D-1238,                                                                            D-638                                                                              D-790 D-1525                                                                             D-2240                                                   190° C.                                               5980 20.0  0.958 300.0                                                                              --   4800  43   50                                      5990 20.0  0.955 1300.0                                                                             650  2600  40   42                                      5990 20.0  0.955 1300.0                                                                             650  3200  40   42                                      5981 20.0  0.960 300.0                                                                              900  3200  46   48                                      5981 20.0  0.960 300.0                                                                              900  3200  46   48                                      5983 20.0  0.958 500.0                                                                              850  3100  44   45                                      5991 20.0  0.953 2600.0                                                                             635  2600  38   40                                      __________________________________________________________________________

Due to the high molecular weight of the Primacor 5981 grade of theethylene-acrylic acid copolymer, this copolymer is the more preferredgrade utilized in the invention.

The metal cation salts utilized in the invention are those salts whichprovide the metal cations capable of neutralizing, to various extents,the carboxylic acid groups of the high acid copolymer. These includeacetate, oxide or hydroxide salts of lithium, calcium, zinc, sodium,potassium, nickel, magnesium, and manganese.

Examples of such lithium ion sources are lithium hydroxide monohydrate,lithium hydroxide, lithium oxide and lithium acetate. Sources for thecalcium ion include calcium hydroxide, calcium acetate and calciumoxide. Suitable zinc ion sources are zinc acetate dihydrate and zincacetate, a blend of zinc oxide and acetic acid. Examples of sodium ionsources are sodium hydroxide and sodium acetate. Sources for thepotassium ion include potassium hydroxide and potassium acetate.Suitable nickel ion sources are nickel acetate, nickel oxide and nickelhydroxide. Sources of magnesium include magnesium oxide, magnesiumhydroxide, magnesium acetate. Sources of manganese include manganeseacetate and manganese oxide.

The new metal cation neutralized high acid ionomer resins are producedby reacting the high acid base copolymer with various amounts of themetal cation salts above the crystalline melting point of the copolymer,such as at a temperature from about 200° F. to about 500° F., preferablyfrom about 250° F. to about 350° F. under high shear conditions at apressure of from about 10 psi to 10,000 psi. Other blending techniquesmay also be used. The amount of metal cation salt utilized to producethe new metal cation neutralized high acid based ionomer resins is thequantity which provides a sufficient amount of the metal cations toneutralize the desired percentage of the carboxylic acid groups in thehigh acid copolymer. The extent of neutralization is generally fromabout 10% to about 90%.

When the acid groups of copolymers of acrylic acid and ethylene sold byThe Dow Chemical Co. (Midland, Mich.) and designated as "Primacor 5981"were neutralized to various weight percentages using a number ofdifferent cations, a number of different high acid ionomer resins wereproduced. Due to differences in the nature of the cation salts, theamount of cation salts utilized, etc., the new high acid ionomer resinsproduced differed substantially in the extent of neutralization and inmelt indices, as well as in resilience (i.e. C.O.R.) and hardnessvalues.

For the purpose of determining the weight percent of neutralization ofthe carboxylic acid groups in the acrylic acid/ethylene copolymer afterreacting with various cation salts, it was assumed that one mole ofsodium (Na⁺), potassium (K⁺), and lithium (Li⁺) neutralized one mole ofacrylic acid, and that one mole of zinc (Zn²⁺), magnesium (Mg²⁺),manganese (Mn²⁺), calcium (Ca²⁺) and nickel (Ni²⁺) neutralized two molesof acrylic acid. The calculations of neutralization were based upon anacrylic acid molecular weight of 79 g/m, giving 0.2778 moles per 100grams of copolymer.

As indicated below in Table 4, the various cation salts were added invariable amounts to the 20 weight percent acrylic acid/ethylenecopolymer in order to determine the optimal level of neutralization foreach of the cations. In Table 4, NaOH refers to sodium hydroxide(formula weight of 40). MnAc refers to manganese acetate tetrahydratehaving a formula weight of 245. LiOH is lithium hydroxide, fwt=24. KOHis potassium hydroxide, fwt=56. ZnAc is zinc acetate dihydrate,fwt=219.5. MgAc is magnesium acetate tetrahydrate, fwt=214.4. CaAc iscalcium acetate, fwt=158. MgO is magnesium oxide, fwt=40.3. NiAc isnickel acetate, fwt=176.8. All of these cation salts are solids at roomtemperature.

The specific cation salts were added in differing amounts with the 20weight percent acrylic acid/ethylene copolymer (i.e. the Primacor 5981)to an internal mixer (Banbury type) for the neutralization reaction. Theonly exception was calcium acetate, which, due to problems encounteredin solid form, was added as a 30 wt % solution in water.

In the neutralization reaction, the cation salts solubilized in thePrimacor 5981 acrylic acid/ethylene copolymer above the melting point ofthe copolymer and a vigorous reaction took place with a great deal offoaming occurring as the cation reacted with the carboxylic acid groupsof the acrylic acid/ethylene copolymer and the volatile by-products ofwater (in the case of oxides or hydroxides) or acetic acid (whenacetates are used) were evaporated. The reaction was continued untilfoaming ceased (i.e. about 30-45 minutes at 250-350° F.), and the batchwas removed from the Banbury mixer. Mixing continued of the batchobtained from the mixer on a hot two-roll mill (175-250° F.) to completethe neutralization reaction. The extent of the reaction was monitored bymeasuring melt flow index according to ASTM D-1238-E. As indicatedbelow, the neutralized products exhibited different properties dependingupon the nature and amount of the cation salts utilized.

                  TABLE 4                                                         ______________________________________                                        Formulation                                                                           Wt % Cation                                                                             Wt %       Melt       Shore D                               No.     Salt      Neutralization                                                                           Index                                                                              C.O.R.                                                                              Hardness                              ______________________________________                                        1(NaOH) 6.98      67.5       0.9  .804  71                                    2(NaOH) 5.66      54.0       2.4  .808  73                                    3(NaOH) 3.84      35.9       12.2 .812  69                                    4(NaOH) 2.91      27.0       17.5 .812  (brittle)                             5(MnAc) 19.6      71.7       7.5  .809  73                                    6(MnAc) 23.1      88.3       3.5  .814  77                                    7(MnAc) 15.3      53.0       7.5  .810  72                                    8(MnAc) 26.5      106        0.7  .813  (brittle)                             9(LiOH) 4.54      71.3       0.6  .810  74                                    10(LiOH)                                                                              3.38      52.5       4.2  .818  72                                    11(LiOH)                                                                              2.34      35.9       18.6 .815  72                                    12(KOH) 5.30      36.0       19.3 Broke 70                                    13(KOH) 8.26      57.9       7.18 .804  70                                    14(KOH) 10.7      77.0       4.3  .801  67                                    15(ZnAc)                                                                              17.9      71.5       0.2  .806  71                                    16(ZnAc)                                                                              13.9      53.0       0.9  .797  69                                    17(ZnAc)                                                                              9.91      36.1       3.4  .793  67                                    18(MgAc)                                                                              17.4      70.7       2.8  .814  74                                    19)MgAc)                                                                              20.6      87.1       1.5  .815  76                                    20(MgAc)                                                                              13.8      53.8       4.1  .814  74                                    21(CaAc)                                                                              13.2      69.2       1.1  .813  74                                    22(CaAc)                                                                              7.12      34.9       10.1 .808  70                                    ______________________________________                                         Controls: 50/50 Blend of loteks 8000/7030 C.O.R. = .810/65 Shore D            Hardness                                                                      DuPont High Acid Surlyn ® 8422 (Na) C.O.R. = .811/70 Shore D Hardness     DuPont High Acid Surlyn ® 8162 (Zn) C.O.R. = .807/65 Shore D Hardness     Exxon High Acid lotek EX960 (Zn) C.O.R. = .796/65 Shore D Hardness       

    ______________________________________                                        Formulation                                                                           Wt % Cation                                                                             Wt %       Melt       Shore D                               No.     Salt      Neutralization                                                                           Index                                                                              C.O.R.                                                                              Hardness                              ______________________________________                                        23(MgO) 2.91      53.5       2.5  .813                                        24(MgO) 3.85      71.5       2.8  .808                                        25(MgO) 4.76      89.3       1.1  .809                                        26(MgO) 1.96      35.7       7.5  .815                                        ______________________________________                                         Control for Formulation 23-                                                  26 is 50/50 lotek 8000/7030, C.O.R. = .814                                     Formulation 26 C.O.R. was normalized to that control accordingly.        

    ______________________________________                                        Formulation                                                                           Wt % Cation                                                                             Wt %       Melt       Shore D                               No.     Salt      Neutralization                                                                           Index                                                                              C.O.R.                                                                              Hardness                              ______________________________________                                        27(NiAc)                                                                              13.04     61.1       0.2  .802  71                                    28(NiAc)                                                                              10.71     48.9       0.5  .799  72                                    29(NiAc)                                                                               8.26     36.7       1.8  .796  69                                    30(NiAc)                                                                               5.66     24.4       7.6  .786  64                                    ______________________________________                                         Control for formulation No. 27-30 is 50/50 lotek 8000/7030, C.O.R. = .807

When compared to low acid versions of similar cation neutralized ionomerresins, the new metal cation neutralized high acid ionomer resinsexhibit enhanced hardness, modulus and resilience characteristics. Theseare properties that are particularly desirable in a number ofthermoplastic fields, including the field of golf ball manufacturing.

As will be further noted in the Examples below, either or both high andlow acid ionomer resins may be used in the cover compositions so long asthe molded cover produces a Shore D hardness of 64 or more. Propertiesof some low acid ionomer resins are provided in the following table:

                                      TABLE 5                                     __________________________________________________________________________    Typical Properties of lotek lonomers                                          __________________________________________________________________________    Resin       ASTM                                                              Properties  Method                                                                            Units                                                                              4000                                                                              4010 8000                                                                              8020                                                                              8030                                    __________________________________________________________________________    Cation Type          zinc                                                                              zinc sodium                                                                            sodium                                                                            sodium                                  Melt Index  D-1238                                                                            g/10 min.                                                                          2.5 1.5  0.8 1.6 2.8                                     Density     D-1505                                                                            kg/m.sup.3                                                                         963 963  954 960 960                                     Melting Point                                                                             D-3417                                                                            ° C.                                                                        90  90   90  87.5                                                                              87.5                                    Crystallization Point                                                                     D-3417                                                                            ° C.                                                                        62  64   56  53  55                                      Vicat Softening Point                                                                     D-1525                                                                            ° C.                                                                        62  63   61  64  67                                      % Wt Acrylic Acid    16       11                                              % of Acid Groups     30       40                                              cation neutralized                                                            __________________________________________________________________________    Plaque                                                                        Properties           4000                                                                              4010 8000                                                                              8020                                                                              8030                                    __________________________________________________________________________    (3 mm thick,                                                                  compression molded)                                                           Tensile at break                                                                          D-638                                                                             MPa  24  26   36  31.5                                                                              28                                      Yield point D-638                                                                             MPa  none                                                                              none 21  21  23                                      Elongation at break                                                                       D-638                                                                             %    395 420  350 410 395                                     1% Secant modulus                                                                         D-63B                                                                             MPa  160 160  300 350 390                                     Shore Hardness D                                                                          D-2240                                                                            --   55  55   61  58  59                                      __________________________________________________________________________    Film Properties      4000                                                                              4010 8000                                                                              8020                                                                              8030                                    __________________________________________________________________________    (50 micron film 2.2:1                                                         Blow-up ratio)                                                                Tensile at Break                                                                       MD D-882                                                                             MPa  41  39  42  52  47.4                                              TD D-882                                                                             MPa  37  38  38  38  40.5                                     Yield Point                                                                            MD D-882                                                                             MPa  15  17  17  23  21.6                                              TD D-882                                                                             MPa  14  15  15  21  20.7                                     Elongation at Break                                                                    MD D-882                                                                             %    310 270 260 295 305                                               TD D-882                                                                             %    360 340 280 340 345                                      1% Secant modulus                                                                      MD D-882                                                                             MPa  210 215 390 380 380                                               TD D-882                                                                             MPa  200 225 380 350 345                                      Dart Drop Impact                                                                          D-1709                                                                            g/micron                                                                           12.4                                                                              12.5                                                                              20.3                                             __________________________________________________________________________                ASTM                                                              Resin Properties                                                                          Method                                                                            Units                                                                              7010                                                                              7020                                                                              7030                                             __________________________________________________________________________    Cation type          zinc                                                                              zinc                                                                              zinc                                             Melt Index  D-1238                                                                            g/10 min.                                                                          0.8 1.5 2.5                                              Density     D-1505                                                                            kg/m.sup.3                                                                         960 960 960                                              Melting Point                                                                             D-3417                                                                            ° C.                                                                        90  90  90                                               Crystallization Point                                                                     D-3417                                                                            ° C.                                                                        --  --  --                                               Vicat Softening Point                                                                     D-1525                                                                            ° C.                                                                        60  63  62.5                                             % Wt Acrylic Acid    --  --  --                                               % of Acid Groups     --  --  --                                               cation neutralized                                                            __________________________________________________________________________                ASTM                                                              Plaque Properties                                                                         Method                                                                            Units                                                                              7010                                                                              7020                                                                              7030                                             __________________________________________________________________________    (3 mm thick,                                                                  compression molded)                                                           Tensile at break                                                                          D-638                                                                             MPa  38  38  38                                               Yield Point D-638                                                                             MPa  none                                                                              none                                                                              none                                             Elongation at break                                                                       D-638                                                                             %    500 420 395                                              1% Secant modulus                                                                         D-638                                                                             MPa  --  --  --                                               Shore Hardness D                                                                          D-2240                                                                            --   57  55  55                                               __________________________________________________________________________

Additional materials may also be added to the cover (or inner and outercover layers) of the present invention as long as they do notsubstantially reduce the playability properties of the ball. Suchmaterials include dyes (for example, Ultramarine Blue sold by Whitaker,Clark, and Daniels of South Plainsfield, N.J.) (see U.S. Pat. No.4,679,795), optical brighteners, pigments such as titanium dioxide, zincoxide, barium sulfate and zinc sulfate; UV absorbers; antioxidants;antistatic agents; and stabilizers. Moreover, the cover compositions ofthe present invention may also contain softening agents such as thosedisclosed in U.S. Pat. Nos. 5,312,857 and 5,306,760, includingplasticizers, metal stearates, processing acids, etc., and reinforcingmaterials such as glass fibers and inorganic fillers, as long as thedesired properties produced by the golf ball covers of the invention arenot impaired.

Moreover, since there are various hues of white, i.e. blue white, yellowwhite, etc., trace amounts of blue pigment may be added to the coverstock composition to impart a blue white appearance thereto. However, ifdifferent hues of the color white are desired, different pigments can beadded to the cover composition at the amounts necessary to produce thecolor desired.

In addition, it is within the purview of this invention to add to thecover compositions of this invention compatible materials such asantioxidants (i.e. Santonox R), antistatic agents, stabilizers andprocessing aids. The cover compositions of the present invention mayalso contain softening agents, such as plasticizers, etc., andreinforcing materials such as glass fibers and inorganic fillers, aslong as the desired properties produced by the golf ball covers of theinvention are not impaired.

Furthermore, optical brighteners, such as those disclosed in U.S. Pat.No. 4,679,795, may also be included in the cover composition of theinvention. Examples of suitable optical brighteners which can be used inaccordance with this invention are Uvitex OB as sold by the Ciba-GeigyChemical Company, Ardsley, N.Y. Uvitex OB thought to be2,5-Bis(5-tert-butyl-2-benzoxazoyl)-thiophene. Examples of other opticalbrighteners suitable for use in accordance with this invention includeLeucopure EGM as sold by Sandoz, East Hanover, N.J. 07936. Leucopure EGMis thought to be 7-(2n-naphthol(1,2-d)-triazol-2yl(3phenyl-coumarin.Phorwhite K-20G2 is sold by Mobay Chemical Corporation, P.O. Box 385,Union Metro Park, Union, N.J. 07083, and is thought to be a pyrazolinederivative. Eastobrite OB-1 is2,2'(1,2-ethenediyldi-4,1-phenylene)bisbenzoxazole and is available fromEastman Chemical Company.

Moreover, since many optical brighteners are colored, the percentage ofoptical brighteners utilized must not be excessive in order to preventthe optical brightener from functioning as a pigment or dye in its ownright.

The percentage of optical brighteners which can be used in accordancewith this invention is from about 0.01% to about 0.5% as based on theweight of the polymer used as a cover stock. A more preferred range isfrom about 0.05% to about 0.25% with the most preferred range from about0.10% to about 0.20% depending on the optical properties of theparticular optical brightener used and the polymeric environment inwhich it is a part.

Generally, the additives are admixed with a ionomer to be used in thecover composition to provide a masterbatch (M.B.) of desiredconcentration and an amount of the masterbatch sufficient to provide thedesired amounts of additive is then admixed with the copolymer blends.

The above cover compositions, when combined with soft cores at thethicknesses described herein, produce golf balls having a relatively lowspin in combination with good click and feel.

The cover compositions and molded balls of the present invention may beproduced according to conventional melt blending procedures. In thisregard, the ionomeric resins are blended along with the masterbatchcontaining the desired additives in a Banbury® type mixer, two-rollmill, or extruded prior to molding. The blended composition is thenformed into slabs or pellets, etc. and maintained in such a state untilmolding is desired. Alternatively a simple dry blend of the pelletizedor granulated resins and color masterbatch may be prepared and feddirectly into the injection molding machine where homogenization occursin the mixing section of the barrel prior to injection into the mold. Ifnecessary, further additives such as an inorganic filler, etc., may beadded and uniformly mixed before initiation of the molding process.

Moreover, golf balls of the present invention can be produced by moldingprocesses currently well known in the golf ball art. Specifically, thegolf balls can be produced by conventional molding techniques, such asby injection molding or compression molding the novel cover compositionsover the soft polybutadiene cores to produce a golf ball having adiameter of about 1.680 inches or greater, preferably at least 1.70inches, and weighing about 1.620 ounces. Larger molds are utilized toproduce the thicker covered oversized golf balls. For injection-moldedcovers having a thickness of up to about 3.0 mm, it may be preferable tomold the cover in a single step. For covers of 3.0 mm or more, it may bepreferable for reasons of both processability and uniformity to mold thecover in two layers. In compression molding, it may be appropriate tomold a thicker cover in a single layer. In compression molding, thecover composition is formed via injection at about 380° F. to about 450°F. into smooth surfaced hemispherical shells which are then positionedaround the core in a dimpled golf ball mold and subjected to compressionmolding at 200°-300° F. for 2-10 minutes, followed by cooling at 50°-70°F. for 2-10 minutes, to fuse the shells together to form an unitaryball. In addition, the golf balls may be produced by injection molding,wherein the cover composition is injected directly around the coreplaced in the center of a golf ball mold for a period of time at a moldtemperature of from 50° to about 100° F. After molding the golf ballsproduced may undergo various further finishing steps such as flashtrimming, priming, marking, finish coating and the like as is well knownand is disclosed, for example in U.S. Pat. No. 4,911,451.

The present invention is further illustrated by the following examplesin which the parts of the specific ingredients are by weight (pbw). Itis to be understood that the present invention is not limited to theexamples, and various changes and modifications may be made in theinvention without departing from the spirit and scope thereof.

EXAMPLE 1

A number of golf ball cores having Formulation A, shown below, wereprepared.

    ______________________________________                                        Core Formulation A                                                                            Parts by                                                      Material        Weight                                                        ______________________________________                                        SMR - CV 60.sup.1                                                                             25.00                                                         Taktene 220.sup.2                                                                             73.50                                                         Hi-Sil 234 LD.sup.3                                                                           6.00                                                          Zinc Oxide.sup.4                                                                              5.00                                                          Barytes #22.sup.5                                                                             80.00                                                         Stearic Acid.sup.6                                                                            1.60                                                          Agerite Superlite.sup.7                                                                       1.60                                                          TiO.sub.2 Rutile 2020.sup.8                                                                   3.00                                                          Circolite Oil.sup.9                                                                           5.00                                                          Red pigment.sup.10                                                                            3                                                             Sulfur (insol).sup.11                                                                         3.14                                                          Santocure N.S..sup.12                                                                         1.28                                                          Methyl Zimate.sup.13                                                                          0.27                                                          D.P.G..sup.14   0.68                                                                          206.07                                                        ______________________________________                                         .sup.1 Natural rubber, Muehlstein, Norwalk, CT                                .sup.2 Synthetic polybutadiene, Bayer Corp., Akron, OH                        .sup.3 Precipitated hydrated silica, PPG Industries, Pittsburg, PA            .sup.4 Zinc Corp. of America, Monaca, PA                                      .sup.5 Harwick Chemical, Akron, OH                                            .sup.6 Harwick Chemical, Akron, OH                                            .sup.7 R.T. Vanderbilt, Norwalk, CT                                           .sup.8 Harwick Chemical, Akron, OH                                            .sup.9 Sun Oil, Philadelphia, PA                                              .sup.10 Stauffer Chemical, Westport, CT                                       .sup.11 Stauffer Chemical, Westport, Ct                                       .sup.12 R.T. Vanderbilt, Norwalk, CT                                          .sup.13 R.T. Vanderbilt, Norwalk, CT                                          .sup.14 1,3Diphenylguanidine (accelerator) R.T. Vanderbilt, Norwalk, CT  

One to two dozen cores were made having a diameter of 36.3 mm (1.430inches) (Example 1-1). One to two dozen cores having a diameter of 37.3mm (1.470 inches) also were made (Example 1-2). The 36.3 mm diametercores were cured at 320° F. for 12 minutes, followed by six minutes ofcooling using cooling water. The cores having a 37.3 mm diameter werecured at 320° F. for 12 minutes, followed by six minutes of coolingusing cooling water. The cores were covered with a single layer of anionomeric cover material having Cover Formulation W, shown below:

    ______________________________________                                        Cover Formulation W                                                                    Parts by              Parts by                                                weight   White Masterbatch                                                                          weight                                         ______________________________________                                        lotek 8000 70.6       lotek 7030   100                                        lotek 7010 19.9       Unitane 0-110                                                                              31.72                                      White MasterBatch                                                                         9.5       Ultra Marine Blue                                                                          0.6                                                              Eastobrite OB-1                                                                            0.35                                                             Santonox R   0.05                                       ______________________________________                                    

As shown on Table 6 below, the golf balls with a 36.3 mm core diameterhad an overall weight of 43.5 grams, a cover thickness of 3.68 mm (0.145inches), a PGA compression of 78, and a coefficient of restitution of0.744 (Example 1-1). The golf balls with 37.3 mm (1.470 inch) cores hada weight of 44.4 grams, a cover thickness of 3.17 mm (0.125 inches), aPGA compression of 48, and a coefficient of restitution of 0.732(Example 1-2). These golf balls have excellent feel due to thecombination of a hard cover and a very soft core, and could be used asrestricted flight golf balls.

A number of golf ball cores having Core Formulation B, shown below, wereformed.

    ______________________________________                                        Core Formulation B                                                                                  Parts by                                                Material              Weight                                                  ______________________________________                                        Cariflex BR-1220.sup.1                                                                              67.35                                                   Taktene 220.sup.2     27.50                                                   Natsyn 2200.sup.3     5.15                                                    Zinc Oxide.sup.4      6.53                                                    Limestone.sup.5       8.25                                                    Poly Pro 20 Mesh.sup.6                                                                              6.19                                                    Regrind.sup.7         19.59                                                   Zinc Stearate.sup.8   14.78                                                   Zinc Diacrylate.sup.9 19.24                                                   Lupersol 230XL OR Triganox 17/40.sup.10                                                             1.48                                                    ______________________________________                                         .sup.1 Polybutadiene Muehlstein, Norwalk, CT                                  .sup.2 Synthetic Polybutadiene Bayer Corp., Akron, OH                         .sup.3 Natural Rubber Muehlstein, Norwalk, CT                                 .sup.4 Zinc Corp of America, Monaca, PA                                       .sup.5 Lee Lime, Lee, MA                                                      .sup.6 Amoco Chemical                                                         .sup.7 golf ball core regrind (internal source)                               .sup.8 Synpro, Cleveland, OH                                                  .sup.9 Rockland React Rite, Rockland, GA                                      .sup.10 peroxide, R.T. Vanderbilt, Norwalk, CT                           

The cores were cured for 15 minutes at 310° F. followed by 7 minutes ofcooling using cooling water. Cores having diameters of 36.3 mm (1.430inches) (Example 1-4) and of 37.3 mm (1.470 inches) were formed (Example1-3). Cores having a diameter of 39.2 mm (1.545 inches) also were formed(Example 1-C1) as a control. The cores of Examples 1-3, 1-4 and 1-C1were covered with a single layer of the same ionomeric cover material aswas used in Examples 1-1 and 1-2. The 36.3 mm and 37.3 mm diameter coresresulted in golf balls having an overall diameter of 43.7 mm (1.72inches) (Examples 1-3 and 1-4). The 39.2 mm cores were used to form golfballs having a diameter of 43.8 mm (1.725 inches) (Example 1-C1).

The golf balls made from 36.3 mm cores (Example 1-4) had a final weightof 44.5 grams, a cover thickness of 3.68 mm (0.145 inches), a PGAcompression of 112 and a coefficient of restitution of 0.811. The ballsmade from 37.3 mm cores (Example 1-3) had a weight of 45.1 grams, acover thickness of 3.18 mm (0.124 inches), a PGA compression of 105, anda coefficient of restitution of 0.809. The control balls having 39.2 mmcores (Example 1-C1) had an overall weight of 46.0 grams, a coverthickness of 2.29 mm (0.090 inches), a PGA compression of 93, and acoefficient of restitution of 0.812. This Example shows that with thethick covered golf ball of the invention, PGA compression increases withcover thickness, while resulting in only a small change in COR.

EXAMPLE 2

A number of 32.8 mm (1.29 inch) diameter golf ball cores were made usingCore Formulation C, shown below. The curing process was the same as thesulfur curing process described above in Example 1. The cores were usedto make four different types of golf balls having the cover compositionsand thicknesses shown on Table 6 as Examples 2-1 to 2-4. The lotek959/960 formulation (Cover Formulation X) also is shown below.

    ______________________________________                                        Core Formulation C                                                                              Cover Formulation X                                                   Parts by             Parts by                                                 Weight               Weight                                         ______________________________________                                        Cariflex BR 1220                                                                          80        lotek 959    45.3                                       SMR CV 60   20        lotek 960    45.3                                       Zinc Oxide  5         White MasterBatch                                                                           9.4                                       Limestone   110       (see formulation in Ex. 1)                              Stearic Acid                                                                                1.6                                                             Agerite Superlite                                                                           1.6                                                             Circolite Oil                                                                             5                                                                 Sulfur        3.14                                                            Santocure N.S.                                                                              1.28                                                            Methyl Zimate                                                                               0.28                                                            D.P.G.        0.68                                                                         228.58                                                           ______________________________________                                    

The resulting PGA compression and coefficient of restitution of the golfballs also is shown on Table 6. A control example using a 39.2 mm (1.545inch) core having Core Formulation I, shown below, and a single coverlayer with a thickness of 1.78 mm (0.070 inches) also was formed. Thephysical properties of the resulting balls are shown on Table 6 as 2-C1.

    ______________________________________                                        Core Formulation I                                                                              Parts by Weight                                             ______________________________________                                        Cariflex BR-1220    70.80                                                     Taktene 220         29.20                                                     Zinc Oxide          6.93                                                      Limestone           18.98                                                     Poly Pro 20 Mesh    2.55                                                      Regrind             20.07                                                     Zinc Stearate       20.07                                                     ZDA                 30.29                                                     Blue masterbatch.sup.1                                                                            0.01                                                      Luperco 231-XL OR Triganox 29/40.sup.2                                                            0.90                                                      ______________________________________                                         .sup.1 internal source                                                        .sup.2 peroxide, R.T. Vanderbilt, Norwalk, CT                            

The very thick covered balls had the same overall compression as thethin covered control (2-C1) even though the thick covers were more thandouble the thickness of the control.

EXAMPLE 3

A number of sulfur-cured golf ball cores having a diameter of 32.5 mm(1.28 inches) and the formulation shown below were formed:

    ______________________________________                                        Core Formulation D                                                                   Materials phr                                                          ______________________________________                                               Cariflex BR-1220                                                                        80                                                                  SMR CV-60 20                                                                  Zinc Oxide                                                                              5                                                                   Limestone 20                                                                  Stearic Acid                                                                            1.6                                                                 Circolite oil                                                                           5                                                                   Sulfur    3.14                                                                Santocure N.S.                                                                          1.28                                                                Methyl Zimate                                                                           0.28                                                                D.P.G.    0.68                                                                Agerite White.sup.1                                                                     0.8                                                          ______________________________________                                         .sup.1 R.T. Vanderbilt, Norwalk, CT                                      

The cores were cured for 12 minutes at 320° F., followed by cooling forsix minutes with cooling water. The sulfur-cured cores (Examples 3-3,3-4, 3-7 and 3-8) had a surface Shore A hardness of 71, a Shore Chardness of 35 and a Shore D hardness of 21.

A number of peroxide-cured cores having a diameter of 32.5 mm (1.28inches) and Core Formulation B, shown above were formed. The cores werecured for 15 minutes at 310° F., followed by cooling for seven minutesusing cooling water. The cores (Examples 3-1, 3-2, 3-5 and 3-6) had thePGA compression and COR values shown on Table 6.

A number of "control" cores were made having a diameter of 39.2 mm(1.545 inches) and having Core Formulation F, shown below, were formed(Examples 3-C1 and 3-C2).

    ______________________________________                                        Core Formulation F                                                                              Parts by Weight                                             ______________________________________                                        Cariflex BR-1220    70.37                                                     Taktene 220         29.63                                                     Zinc Oxide          6.67                                                      Limestone           24.07                                                     Poly Pro 20 Mesh    8.89                                                      Regrind             17.04                                                     Zinc Stearate       18.52                                                     Zinc Diacrylate     27.41                                                     Luperco 231-XL or Triganox 17/40                                                                  0.9                                                       ______________________________________                                    

Furthermore, a number of "control" cores having a diameter of 39.2 mm(1.545 inches) and having Core Formulation G, shown below, were formed(Examples 3-C3 and 3-C4).

    ______________________________________                                        Core Formulation G                                                                              Parts by Weight                                             ______________________________________                                        Cariflex BR-1220    73.33                                                     Taktene 220         26.67                                                     Zinc Oxide          22.33                                                     Regrind             10                                                        Zinc Stearate       20                                                        Zinc Diacrylate     26                                                        Luperco 231-XL or Triganox 17/40                                                                  0.9                                                       ______________________________________                                    

The 32.5 mm cores were covered with a 3.35 mm (0.132 inch) thick layerof ionomer followed by a 1.78 mm (0.070 inch) thick layer of the same ora different ionomer. The covers had a "422 tri" dimple pattern, which isthe same dimple pattern as is used on the Top Flite Hot XL (1995), tourtrajectory ball. The compression and coefficient of the cores, ballshaving the first cover layer, and balls having the second cover layer,as well as the finished balls, was obtained and is shown on Table 6. Thecontrol cores were covered with a single layer of ionomer having athickness of 0.070 inches.

EXAMPLE 4

A number of thermoplastic golf ball cores containing 100 parts by weightEXACT 4049 (Exxon Chemical Co.) and 60 parts by weight of tungstenpowder were formed (Core Formulation H, Examples 4-1, 4-2, 4-5 and 4-6).The cores were cured for 5 minutes at 320° F. followed by cooling usingcooling water for 7 minutes. The cores had a weight of 23.3 grams and adiameter of 32.5 mm (1.28 inches). The cores were covered with a 3.35 mm(0.132 inch) thick layer of ionomer, followed by a second cover having athickness of about 1.78 mm (0.070 inches). The inner and outer coverlayers had the formulations shown on Table 1. Cover formulation Y is asfollows:

    ______________________________________                                        Cover Formulation Y                                                                           Parts by Weight                                               ______________________________________                                        lotek 1002        45.3                                                        lotek 1003        45.3                                                        White MasterBatch 9.4                                                          (see formulation in Ex. 1)                                                   ______________________________________                                    

Cover formulation Z is as follows:

    ______________________________________                                        Cover Formulation Z                                                                           Parts by Weight                                               ______________________________________                                        lotek 8000        70.6                                                        lotek 7010        19.9                                                        White MasterBatch 9.5                                                          (see formulation in Ex. 1 )                                                  ______________________________________                                    

A number of crosslinked cores were made using 100 parts by weight ofEXACT 4049 (Exxon Chemical Co.), which is a metallocene catalyzedpolyolefin, 60 parts by weight of tungsten powder and 5 parts by weightTrigonox 17/40 (Core Formulation J, Examples 4-3, 4-4 and 4-7). Thecores were cured for 14 minutes at 320° F. followed by cooling withcooling water for 7 minutes. The cores had a weight of 23.6 grams. Thecores had a diameter of 32.5 mm (1.28 inches), and were covered with thesame types and thicknesses of cover materials as were used for thethermoplastic cores. The cover materials are shown on Table 6. The outercovers of Example 4 employed a "422 Hex" dimple pattern, which is thesame dimple pattern as is used on the Top Flite XL (1996), regulartrajectory ball.

The compression and coefficient values for the balls having a singlecover layer, both cover layers, and finished products were determinedand are shown on Table 6. As shown by the results, the thick coveredballs give relatively soft compression versus the thick covered ballshaving polybutadiene cores, and demonstrate the variety of propertieswhich are possible with the novel constructions of the invention. Theballs of this Example which have cores made of metallocene catalyzedpolyolefin would be useful as range or practice balls, as they have asoft feel and high spin, as well as a very durable, hard cover.

    TABLE 6       - CORE + INNER COVER +      OUTER COVER FINISHED BALL SPIN                   EXAMPLE  Size Comp COR        Thickness Comp COR  Thickness Comp COR Weight Comp COR Revs/       # Type.sup.1 mm (PGA) (× 1000) Type.sup.2 mm (PGA) (×     1000) Type.sup.2 mm (PGA) (× 1000) (g) (PGA) (× 1000)     min       1-1 A 36.322 -- --     W 3.68   43.5 78 744 --       1-2 A 37.338 -- --     W 3.18   44.4 48 732 --       1-3 B 37.338 -- --     W 3.18   45.1 105 809 --       1-4 B 36.322 -- --     W 3.68   44.5 112 811 --       1-C1 B 39.243 -- --     W 2.29   46.0 93 812 --       2-1 C 32.766 -- -- W 3.175 -- -- W 1.778    106 753 --       2-2 C 32.766 -- -- W 3.556 -- -- W 1.397    105 752 --       2-3 C 32.766 -- -- X 3.175 -- -- X 1.778    116 746 --       2-4 C 32.766 -- -- X 3.556 -- -- X 1.397    114 770 --       2-C1 I 39.243 -- -- -- -- -- -- W 1.778    105 803 --       3-1 B 32.512 71 759 X 3.353 115 786 X 1.778 122 791  130 806 6314           3-2 B 32.512 71 759 X 3.353 115 786 W 1.778 118 778  126 796 6095       3-3 D 32.512   X 3.353 75 768 X 1.778 110 769  117 790 --       3-4 D 32.512   X 3.353 75 768 W 1.778 102 764  114 778 --       3-5 B 32.512 71 759 W 3.353 110 772 X 1.778 120 786  128 801 --             3-6 B 32.512 71 759 W 3.353 110 772 W 1.778 118 775  126 791 --       3-7 D 32.512   W 3.353 69 749 X 1.778 108 771  116 776 7999       3-8 D 32.512   W 3.353 69 749 W 1.778 102 756  111 764 --       3-C1 F 39.243 98 762 -- -- -- -- X 1.778 105 790  108 797 --       3-C2 F 39.243 98 762 -- -- -- -- W 1.778 102 789  106 791 --       3-C3 G 39.243 87 767 -- -- -- -- X 1.778 98 800  102 807 --       3-C4 G 39.243 87 767 -- -- -- -- W 1.778 95 789  100 799 --       4-1 H 32.512   Y 3.353 79 731 Y 1.778 103 742 45.4 106 749 8497             4-2 H 32.512   Z 3.353 77 737 Y 1.778 101 746 45.3 105 753 8081       4-3 J 32.512   Y 3.353 80 740 Y 1.778 105 757 46 107 763 8337       4-4 J 32.512   Z 3.353 78 741 Y 1.778 103 759 46.2 105 763 8642             4-5 H 32.512   Y 3.353 79 731 Z 1.778 102 736 45.4 105 743 8226       4-6 H 32.512   Z 3.353 77 737 Z 1.778 99 747 45.2 103 751 8758              4-7 J 32.512   Z 3.353 78 741 Z 1.778 99 751 45.9 104 759     .sup.1 A = sulphur cured core of Ex. 1     B = polybutadiene peroxide cured core of Ex. 1 and Ex. 31, 32, 35 and 36     C = sulphur cured core of Ex. 2     D = sulphur cured core of Ex. 33 and 34     F = polybutadiene peroxide cured core of Ex. 3C1 and 3C2     G = polybutadiene peroxide cured core of Ex. 3C3 and 3C4     H = thermoplastic EXACT core of Ex. 4     I = blue core of Ex. 2     J = thermoset EXACT core of Ex. 4     .sup.2 W = lotek 8000/7030 formulation of Ex. 13     X = lotek 959/960 formulation of Ex. 23     Y = lotek 1002/1003 formulation of Ex. 4     Z = lotek 8000/7010 formulation of Ex. 4

EXAMPLE 5A

The balls of Examples 3-1, 3-2, 3-7, and 4-1 to 4-6 were spin testedunder the following conditions:

Miya Driving Machine

Culb: Top Flite Custom 9 iron

Culb Head Speed: 105 fps

The results are shown on Table 6 above.

The balls of Examples 3-1, 3-2, 3-7, 4-5 and 4-6 were distance testedand were compared with the 1995 Hot XL golf balls. The distance testconditions are provided below:

Club Name: Top Flite Tour 10.5

Club Head Speed: 160 ft/sec

Launch Angle--degrees: 9.5

The distance test results are shown below on Table 7.

                  TABLE 7                                                         ______________________________________                                                     Flight      Carry Ctr        Total                                                                              Total                             Traj Time Carry Diff Dev.sup.1 Roll Dist Diff                                Ball o sec yds yds yds yds yds yds                                          ______________________________________                                        3-1   12.5   10.0   244.4                                                                              0.0   -2.25                                                                              11.3  255.6                                                                              0.0                              3-7 12.8 10.0 237.7 -6.6 -1.75 9.4 247.1 -8.5                                 3-2 12.1 10.0 227.4 -17.0 -3.04 19.2 246.6 -9.1                               4-5 10.9 10.0 225.5 -18.9 -6.54 10.2 235.7 -20.0                              4-6 11.3 9.9 226.8 -17.5 -6.71 11.7 238.5 -17.1                               Hot XL 11.7 10.0 237.8 -6.6 -4.75 13.1 250.9 -4.8                             (1995)                                                                      ______________________________________                                         .sup.1 Deviation from center                                             

The longest ball is that of Example 3-1. This result is surprising,particularly in view of the fact that this ball has a COR of 0.806,while the 1995 Hot XL ball has a COR of 0.812±0.003.

The ball of Example 3-2 had a surprisingly long total distance given itslow COR of 0.776.

EXAMPLE 5B

Distance tests were conducted for the balls of Examples 3-1, 3-2 and 4-1to 4-4 under slightly different conditions, which were the following:

Club Name: Top Flite Tour 10.5

Club Head Speed: 155 ft/sec

Launch Angle--degrees: 9.6

The distance test results are shown below on Table 8.

                  TABLE 8                                                         ______________________________________                                                     Flight      Carry Ctr        Total                                                                              Total                             Traj Time Carry Diff Dev Roll Dist Diff                                      Ball o sec yds yds yds yds yds yds                                          ______________________________________                                        4-1   11.5   9.9    227.1                                                                              -12.2 2.08 13.1  240.2                                                                              -12.9                            4-2 11.9 10.0 226.1 -13.1 1.96 13.4 239.5 -13.6                               4-3 11.8 10.0 228.0 -11.3 2.54 12.1 240.1 -13.0                               4-4 11.8 10.0 227.4 -11.9 0.63 11.1 238.5 -14.6                               3-1 12.0 10.0 239.3 0.0 2.10 13.8 253.1 0.0                                   3-2 12.0 10.0 233.4 -5.9 2.79 11.1 244.5 -8.6                                 Hot XL 12.4 10.0 239.0 -0.2 2.46 13.8 252.9 -0.2                              (1995)                                                                      ______________________________________                                    

Once again, the ball of Example 3-1 is the longest. The ball of Example3-2 again had a surprisingly long total distance given its low COR.

EXAMPLE 6

A number of control golf ball cores having a diameter of 39.2 mm (1.545inches) and a weight of 36.7 g were formed using Core Formulation K,shown below.

    ______________________________________                                        Core Formulation K                                                                           Parts by Weight                                                ______________________________________                                        Cariflex 1220  70                                                               Taktene 220 30                                                                Zinc Oxide 6.7                                                                Zinc diacrylate 27.4                                                          Zinc Stearate 18.5                                                            Limestone 24                                                                  Poly Pro 20 Mesh 8.9                                                          Regrind 17                                                                    Triganox 17/40 0.9                                                          ______________________________________                                    

The cores were cured for 111/2 minutes at 320° F., and were then cooledusing cooling water for about 7 minutes. The cores had a PGA compressionof 95 and a COR of 0.770.

A number of golf ball cores having Core Formulation L (shown below) anddiameters of 34.8 mm (1.37 inches) and 39.9 mm (1.57 inches) wereformed. The cores were cured for 12 minutes at 320° F., followed bycooling using cooling water for about 6 minutes.

    ______________________________________                                        Core Formulation L                                                                          Parts by Weight                                                 ______________________________________                                        Cariflex 1220 100                                                               Stearic Acid 2                                                                Zinc Oxide 4                                                                  Barytes 52                                                                    Hi-Sil 233.sup.1 7.5                                                          Vanox 1290.sup.2 1                                                            Sulfur 5.25                                                                   Durax.sup.3 1.75                                                              DOTG.sup.4 1                                                                  Bismate.sup.5 2.8                                                           ______________________________________                                         .sup.1 P.P.G. Industries                                                      .sup.2 R.T. Vanderbilt                                                        .sup.3 R.T. Vanderbilt                                                        .sup.4 R.T. Vanderbilt                                                        .sup.5 R.T. Vanderbilt                                                   

The cores of control Examples 6-C1, 6-C2 and 6-C3 were covered with asingle cover layer having a thickness of 1.78 mm (0.07 inches). Thecontrol cores were covered with the cover formulations shown on Table 9,which are the same as cover formulations W-Z in Examples 1-4. The coresof Examples 6-1 through 6-10 were covered with inner and outer covershaving the cover formulations and thicknesses shown on Table 9. All ofthe ball of the invention and the control balls were distance testedusing a 5-iron at 128 feet per second and a driver at 160 feet persecond.

As shown on Table 9, while the balls of the invention had substantiallylower coefficients of restitution than the control balls, their distancewas only slightly shorter. Thus, the golf balls of the invention providea greater distance per point of COR as compared to the control balls.

                                      TABLE 9                                     __________________________________________________________________________                                                     5 Iron @                                                                             Driver @                + Inner Cover + Outer Cover Finished Ball 128 fps 160 fps                      Core   Dia.                                                                             Thickness                                                                          Wgt.                                                                             PGA COR     Thickness                                                                          Wgt.                                                                             PGA COR Carry                                                                             Total                                                                            Carry                                                                             Total                                                                          Ex. # Type                                                                   Material mm                                                                   mm g Comp                                                                     × 1000                                                                  Material mm g                                                                 Comp ×                                                                  1000 yds yds                                                                  yds yds           __________________________________________________________________________    6-C1                                                                             K  N.A.                                                                              N.A.                                                                             N.A. N.A.                                                                             N.A.                                                                              N.A.                                                                              Z   1.78 45.4                                                                             104 792 170.1                                                                             172.1                                                                            249.5                                                                             256.6                                                                          6-1 L W 39.2                                                                 3.50 35.8 70                                                                  742 Z 1.7B                                                                    44.6 105 764                                                                  167.6 170.8                                                                   242.8 248.3                                                                    6-2 L Y 39.2                                                                 3.50 35.8 74                                                                  744 Z 1.78                                                                    44.8 108 759                                                                  166.4 168.4                                                                   241.2 246.4       6-3                                                                              L  X   39.2                                                                             3.50 36.3                                                                             88  766 Z   1.78 45 114 771 Not Tested                                                                           Not Tested            6-4                                                                              L  W   39.9                                                                             3.81 37.1                                                                             77  748 Y   1.40 45 107 766 164.5                                                                             167.2                                                                            242.6                                                                             247.8                                                                          6-5 L Y 39.9                                                                 3.81 37.2 82                                                                  756 Y 1.40 45                                                                 109 765 165.5                                                                 169.6 243.1                                                                   247.9                                                                          6-6 L W 39.2                                                                 3.50 35.8 70                                                                  742 Y 1.78                                                                    44.9 107 757                                                                  166.5 167.4                                                                   243.3 247.3                                                                    6-C2 K N.A.                                                                  N.A. N.A.                                                                     N.A. N.A.                                                                     N.A. Y 1.78                                                                   45.7 106 804                                                                  167.5 171.2                                                                   251 256.7                                                                      6-C3 K N.A.                                                                  N.A. N.A.                                                                     N.A. N.A.                                                                     N.A. X 1.78                                                                   45.8 109 807                                                                  168.5 174.4                                                                   252.2 257.4                                                                    6-7 L Y 39.2                                                                 3.50 35.8 78                                                                  744 X 1.78                                                                    45.2 111 779                                                                  169.5 171.9                                                                   245.7 250.1                                                                    6-8 L X 39.2                                                                 3.50 36.3 88                                                                  766 X 1.78                                                                    45.4 116 783                                                                  170.5 170.8                                                                   244.6 249.7                                                                    6-9 L W 39.9                                                                 3.81 37.1 77                                                                  748 X 1.40                                                                    45.3 112 772                                                                  171.5 171.4                                                                   24Z.5 248.1                                                                    6-10 L X                                                                     39.9 3.81                                                                     37.5 92 76B X                                                                 1.40 45.2 118                                                                 774 172.5                                                                     172.7 245.6                                                                   250.3             __________________________________________________________________________

What is claimed is:
 1. A golf ball comprising:a core having acoefficient of restitution of at least 0.650, and a thermoplastic coverhaving a thickness of at least 3.6 mm (0.142 inches) and a Shore Dhardness of at least
 60. 2. A golf ball according to claim 1, whereinthe core has a PGA compression of about 85 or less and the differencebetween the coefficient of restitution of the ball and the coefficientof restitution of the core is at least 0.025.
 3. A golf ball accordingto claim 1, wherein the ball has a diameter of at least about 42.7 mm(1.68 inches).
 4. A golf ball according to claim 1, wherein the ball hasa diameter of at least about 43.2 mm (1.70 inches).
 5. A golf ballaccording to claim 3, wherein the difference between the coefficient ofrestitution of the core and the coefficient of restitution of the ballis at least 0.025.
 6. A golf ball according to claim 3, wherein thedifference between the coefficient of restitution of the core and thecoefficient of restitution of the ball is at least 0.035.
 7. A golf ballaccording to claim 3, wherein the difference between the coefficient ofrestitution of the core and the coefficient of restitution of the ballis at least 0.045.
 8. A golf ball according to claim 1, wherein thecover includes one or more layers, each of which has a Shore D hardnessof at least
 60. 9. A golf ball according to claim 8, wherein the innerand outer cover layers have substantially the same Shore D hardness. 10.A golf ball according to claim 8, wherein the difference between theShore D hardness of the inner cover layer and the Shore D hardness ofthe outer cover layer is no more than
 5. 11. A golf ball according toclaim 8, wherein the difference between the Shore D hardness of theinner cover layer and the Shore D hardness of the outer cover layer isno more than
 2. 12. A golf ball according to claim 1, wherein the corehas a PGA compression of 85 or less.
 13. A golf ball according to claim1, wherein the core has a COR of at least 0.700.
 14. A golf ballaccording to claim 1, wherein the cover has a thickness of at least 4.0mm (0.157 inches).
 15. A golf ball according to claim 1, wherein thecover has a thickness of at least 4.5 mm (0.177 inches).
 16. A golf ballaccording to claim 1, wherein the core comprises at least one memberselected from the group consisting of natural rubber and polybutadiene.17. A golf ball according to claim 1, wherein the core comprises ametallocene catalyzed polyolefin.
 18. A golf ball according to claim 1,wherein the cover comprises a blend of an ionomer with a hardernon-ionic polymer.
 19. A golf ball according to claim 1, wherein thecore is sulfur cured.
 20. A golf ball, comprising:a foamed core having aCOR of at least 0.650, and a thermoplastic cover comprising an ionomerand having a thickness of at least 3.8 mm (0.150 inches) and a Shore Dhardness of at least 60, the ball having a coefficient of restitution ofat least 0.770.
 21. A golf ball according to claim 20, wherein the corehas a PGA compression of no more than
 85. 22. A method of making a golfball, comprising:forming a core having a COR of at least 0.650, andforming a thermoplastic cover over the core, the cover having athickness of at least 3.6 mm (0.142 inches) and a Shore D hardness of atleast
 60. 23. A method according to claim 22, wherein the cover has athickness of at least 3.8 mm.
 24. A method according to claim 22,wherein the cover comprises an ionomer.
 25. The golf ball according toclaim 18, wherein said harder non-ionic polymer is selected from thegroup consisting of nylon, polyphenylene oxide and metallocene catalyzedpolyolefin.